Recognizing, Evaluating, and Controlling Chemical Hazards to Reduce Occupational Exposure to Hazardous Waste in Academic Laboratories By: Steve Rupkey, CIH Safety/QA Manager Argonne National Laboratory AGENDA Background Anticipation & Recognition Evaluation Control Disclaimer Toxicology Qualitative Elimination Take A Way Health Effects Quantitative Engineering Overview of IH Routs of Entry Administrative Responsibility Exposure Limits PPE Characteristics 2 DISCLAIMER Not covering every IH concept or all hazard types, e.g. – – – – – – Ye Olde Disclaimer Physical & Health Hazards Electrical Safety Noise Radiation Ergonomics Emergency Response For informational purposes only. Your Site ESH professional is your best resource! 3 TAKE A WAY Apply industrial hygiene concepts Predict your exposure to airborne hazardous waste ANTICIPATION RECOGNITION EVALUATION CONTROL 4 INDUSTRIAL HYGIENE Four Fundamental Elements ANTICIPATION RECOGNITION EVALUATION 5 CONTROL INDUSTRIAL HYGIENE Anticipation – Proactive ANTICIPATION RECOGNITION EVALUATION CONTROL Anticipation/recognition of potential or actual hazards • “cradle-to-grave” concept (research through waste disposal) 6 INDUSTRIAL HYGIENE Recognition – Judgment of Exposure Potential ANTICIPATION RECOGNITION EVALUATION CONTROL Anticipation/recognition of potential or actual hazards through knowledge of: • Draws upon your knowledge of Materials – Operations – Processes – Conditions 7 INDUSTRIAL HYGIENE Evaluation – Stressor and ANTICIPATION RECOGNITION EVALUATION CONTROL Evaluation of the level of risk: • • • • Measurement of exposure intensity Determination of exposure frequency, and duration Comparison with regulatory, professional, and internal standards Judgment: weigh all factors 8 INDUSTRIAL HYGIENE Control – Prevention ANTICIPATION RECOGNITION EVALUATION Methods to eliminate or reduce exposure • • • • Elimination / Substitution Engineering Controls Administrative Controls PPE 9 CONTROL INDUSTRIAL HYGIENE Estimating Risk of Exposures Need to understand • Toxicity • Physical and Chemical properties • Manner and quantity handled These factors help determine: • • • • How much enters the body Route of entry into the body Frequency of exposure Duration of exposure 10 RESPONSIBILITY Teamwork keeps everyone safe and healthy Researchers, HSE personnel and contractors are the frontline persons responsible for meeting this goal. Examples of HSE programs that are critical to meeting this goal: • • • • • • RCRA – Marking, Handling and Storage DOT – Shipping Hazardous Materials OSHA 1910.120(q) – Emergency Response Chemical Hygiene Plan – Waste handling Hazard Communication – Understanding the hazards Personal Protective Equipment – Last line of protection 11 ANTICIPATION / RECOGNITIION You need an understanding of .... Toxicology / Health Effects – How material effects the body Routs of Entry – How it enters the body Exposure Limits - How much is allowed Physical Properties of Chemicals – How will it behave 12 TOXICOLOGY Dose Makes The Poison “All chemicals are poisons, there are none that are not. The difference between a cure and a poison is the dose” Paracelsus (14931541) 13 TOXICOLOGY Exposure VS. Absorbed Dose Exposure - substance available for potential contact with the body Environmental Stressors EXPOSURE DOSE • Intensity • Frequency • Duration Absorbed Dose • Bioavailability • Genetics • Susceptibility Routes of Entry Absorbed Dose - amount of substance that contacts the body and is available to cause a reaction 14 TOXICOLOGY Toxicity VS. Hazard VS. Risk Toxicity Degree to which a substance can harm an exposed organism. Hazard Potential for a substance to cause harm (toxicity + dose) Risk Measurement or estimate of hazard 15 TOXICOLOGY What more toxic, hazardous and riskier? What’s more toxic • Mercury vapors • Sodium chloride (table salt) What’s more hazardous? • Putting a thermometer in your mouth • Ingesting 2 pounds of sodium chloride What’s more risky? • It depends 16 TOXICOLOGY Dose-Response Relationship LD50 (Percent) Response 100 NOEL = Highest data point at which there was not an observed affect of interest LOEL 50 LOEL = Lowest data point at which there was an observed affect of interest NOEL 0 0 5 10 15 20 25 30 35 Dose (mg/kg body weight) 40 45 TOXICOLOGY Response depends on many factors • Dose • Rate of generation • Physical state • Temperature • Genetics • Site of contact with body • General health of individual 18 ACUTE EFFECTS High concentration, short duration, short response time Skin irritation - Reversible damage - Acetonitrile (Skin irritation – 3)* Skin corrosion - Irreversible tissue damage - Grignard reagents (Skin corrosion - 1B)* Eye Irritation – Reversible damage - Graphite flakes (Eye Irritation - 1B)* Serious Eye Damage – Irreversible tissue damage - Hydrazine (Seri Eye Dam - 1)* *Source: Sigma Aldrich 2012 HazCom Terms ACUTE EFFECTS Acute Toxicity (Oral, Dermal, Inhalation) Single or multiple dose of a substance ~ 4- 24 hrs. Cat 1: LD50 (oral) -- oral dose/rats ≤ 5 milligrams per kilogram (mg/kg) - Dimethyl mercury (Acute Tox – 1, Dermal)* Cat 2: LD50 (oral) -- oral dose/rats > 5 and ≤ 50 mg/kg - Mercury nitrate monohydrate (Acute Tox – 2, Oral) * Cat 3. LD50 (oral) -- oral dose/rats > 50 and ≤ 300 mg/kg - Nickel chloride (Acute Tox – 3, Oral) * Cat 4. LD50 (oral) -- oral dose/rats > 300 and ≤ 2000 mg/kg - Potassium perchlorate (Acute tox – 4, Oral) * *Source: Sigma Aldrich 2012 HazCom Terms ACUTE EFFECTS Perspective Cat. 1 Cat. 2 Cat. 3 Cat. 4 *Source: Prudent Practices, CHRONIC EFFECTS Low concentration, long-term exposures Carcinogens - Induce cancer or increase its incidence – Benzene (Carcinogen – 1A) * Reproductive – Effects sexual function and fertility and development of the offspring – Karl-Fisher reagent (Reproductive toxicity – 1B) * Mutagens - Inheritable genetic changes, may effect your offspring or their offspring – Benzene (Mutagen – 1B) * *Source: Sigma Aldrich 2012 HazCom Terms 22 ACUTE - CHRONIC EFFECTS Tweeners (my term) Skin Sensitizers - allergic response Respiratory Sensitizers - hypersensitivity of the airways Specific target organ toxicity - single exposure, (STOT-SE) means specific, non- lethal target organ toxicity. Specific target organ toxicity - repeated exposure (STOT-RE) means specific target organ toxicity 23 HEALTH EFFECTS ANTAGONISTIC ADDITIVE SYNERGISTIC 2+2=4 2 + 2 = 10 3 + (-2) = 1 POTENTIATING Exposure to Chemical Combinations 2 + 0 = 10 24 ROUTES OF ENTRY Contact with the body Occupational Routes of Entry • Inhalation • Skin contact/skin absorption • Ingestion • Injection 25 INHALATION Respiratory system – Largest surface area Once inhaled, chemicals are either exhaled or deposited in the respiratory tract. If deposited, damage can occur through direct contact with tissue or the chemical may diffuse into the blood through the lung-blood interface. Upon contact with tissue in the upper respiratory tract or lungs, chemicals may cause health effects ranging from simple irritation to severe tissue destruction. Substances absorbed into the blood are circulated and distributed to organs that have an affinity for that particular chemical. Health effects can then occur in the organs, which are sensitive to the toxicant. 26 SKIN CONTACT / ABSORPTION Largest organ in the body – 2 m2 Skin contact can cause health effects ranging from relatively innocuous (redness or mild dermatitis) to more severe destruction of skin tissue. Many chemicals can also cross the skin barrier and be absorbed into the blood system. Once absorbed, they may produce systemic damage to internal organs The eyes are particularly sensitive to chemicals. Even a short exposure can cause severe effects to the eyes or the substance can be absorbed through the eyes and be transported to other parts of the body causing harmful effects. 27 INGESTION Typically an inadvertent exposure route • Can swallow via mucus from respiratory system • Chemicals that are insoluble in the fluids of the gastrointestinal tract (stomach, small, and large intestines) are generally excreted. • Others that are soluble are absorbed through the lining of the gastrointestinal tract. • They are then transported by the blood to internal organs where they can cause damage. 28 INJECTION Sub cutaneous Substances may enter the body if the skin is penetrated or punctured by contaminated objects. Effects can then occur as the substance is circulated in the blood and deposited in the target organs. 29 FATE Metabolism, storage, and excretion Metabolized - Transformed via chemical reactions in the body Stored in specific organs - Storage may reduce metabolism and therefore, increase the persistence of the chemicals in the body. Excreted - The various excretory mechanisms (exhaled breath, perspiration, urine, feces, or detoxification) rid the body, over a period of time, of the chemical. For some chemicals elimination may be a matter of days or months; for others, the elimination rate is so low that they may persist in the body for a lifetime and cause deleterious effects. 30 EXPOSURE LIMITS Established for many, not all The concentration to which nearly all healthy workers may be repeatedly exposed, day after day, without adverse health effects. 31 EXPOSURE LIMITS Limitations NOT a relative index of toxicity NOT a fine line between healthy and unhealthy NOT protective of all workers Below Healthy E L x u i p r m o e i s t 32 Above Unhealthy EXPOSURE LIMITS Also for physical hazards • • • • • • Noise Heat Stress Cold Stress Vibrations Ionizing Radiation Non-Ionizing Radiation 33 EXPOSURE LIMITS General units of substance allowed in air Gases / Vapors (ppm) • parts per million Particulates / Aerosols (mg/m3) • milligrams per cubic meter Fibers (f/cc) • fibers per cubic centimeter 34 EXPOSURE LIMITS A little perspective A ppm is: – 1/16 of an inch in a mile – 1 penny in $10,000 – 1 minute in two years – 1 dime in a one-mile-high stack of pennies A ppb is: – One drop of ink in the largest tanker trucks used to haul gasoline 35 EXPOSURE LIMITS Primary organization who sets OELs Permissible Exposure Limits (PEL) – The Law Threshold Limit Values (TLV) – Volunteer (best practice) Recommended Exposure Limits (REL) - Volunteer 36 EXPOSURE LIMITS Different types of OELs Time-WeightedAverage (TWA) 8 - hour workday Short-Term Exposure Limits Ceiling Limits (STEL) (C) 15-minutes 15 - minutes 37 Peak 10-minutes EXPOSURE LIMITS Exposures are average concentrations over time sampled Peak 500 ppm Ceiling 200 ppm STEL 150 ppm 8–hr TWA 100 ppm Zero ppm 0 1 2 3 4 HOURS 38 5 6 7 8 EXPOSURE LIMITS Skin (S) notation - TLV There can be a significant exposure due to skin, eye, or mucous membrane contact with the vapors, liquids or solids or by direct contact. Ability to cause irritation, dermatitis, or sensitization is not considered relevant. Excludes irritant or corrosive effects in the absence of systemic toxicity methyl mercury EXPOSURE LIMITS Immediately Dangerous to Life and Health (IDLH) An acute respiratory exposure: • Poses an immediate threat to loss of life, immediate or delayed irreversible adverse effects on health • Acute eye exposure that would prevent escape from a hazardous atmosphere 40 EXPOSURE LIMITS You should try to understand why the OEL was set OEL Substance To Prevent Agency 10 ppm Acetic acid Acute irritation OSHA 50 ppm Carbon monoxide Stress on cardiovascular system OSHA 200 ppm Acetaldehyde Eye irritation OSHA 1000 ppm Acetone CNS (dizziness) OSHA NOT a relative index of toxicity Best Resource: ACGIH’s Documentation of the Threshold Limit Values for Chemical Substances and Physical Agents & Biological Exposure Indices 41 Knowledge of the physical state of matter can help anticipate its movement in the air near your “Breathing Zone”. 42 PHYSICAL PROPERTIES Physical States of Matter 43 SOLIDS – Dust and Particulates Dusts Particles from mechanical grinding or crushing Particulates Granular Fine solid or liquid particles • Dust (0.1 – 30 μm) • Mists (0.01 – 10 μm) • Aerosols (0.01 – 10 μm) • Fumes • Smoke C44 SOLIDS – Dust and Particulates Have a large combined surface area Can: • Behave like gases • Stay airborne for long periods • Easily be inhaled • Form explosive mixtures • Be toxic and corrosive • Be combustible and flammable • Slough off material when handled 45 LIQUIDS Viscosity The state of being thick, sticky, and semifluid in consistency, due to internal friction. Low Viscosity • Acetone • Milk • Water High Viscosity • Oil • Gelatinous • Paste C46 LIQUIDS Liquids flow Can: • Be toxic and corrosive • Be absorbed through the skin and mucus membranes • Cause contact related health effects 47 VAPORS Form from solids and liquids Can: Evaporation affected by: • Be absorbed through the skin and mucus membranes • Cause contact related health effects • Form in the head space • Form when chemicals mix • Evaporate to form toxic, corrosive and/or flammable vapors! • Air Speed • Temperatures • Relative Humidity Don’t confuse vapors with “fumes” 48 GASES Fill the space in which it is generated Can: • Can be toxic and/or corrosive • Flammable or cryogenic • Can be lighter than air • Can be heavier than air 49 VAPOR PRESSURE Tendency to evaporate and become a gas Usually expressed mm Hg The higher the vapor pressure, the greater the tendency of the substance to evaporate Chemical VP mm Hg Temperature (°F) Ethylene Glycol 4 68 Water 18 68 Acetaldehyde 740 68 Nitrous oxide 42453 77 50 Directly related to temp. GAS & VAPOR DENSITY Can be lighter, heavier, or same density as air (air = 1) • Lighter than air (< 1) VD of gasoline = 3 – 4 • Will tend to rise • Where would you expect the vapors to accumulate? • Air (1) (MW = 30) Ventilation plays a role • Heavier than air (> 1) • Will tend to sink 51 COMPATIBILITY Can be a good or bad characteristic When chemicals can remain in contact indefinitely without reaction, they are compatible. May not always produce a hazard. 52 INCOMPATIBILE Can generate and release Flammable vapors Hazardous energies Toxic vapors Sodium hypochlorite Acid Fumes Always know the Chlorine compatibility Hydrogen Halide before Ammonia combining Nitrogen Oxides substances Oxygen 53 Ammonia cameochemicals.noaa.gov/reactivity ANTICIPATION / RECOGNITIION Summary Toxicology Health Effects Exposure Routes Exposure Limits How Chemicals Behave Chemical 54 Compatibility EVALUATION Evaluate your potential exposure Based on your of knowledge: – How stressors might behave – Now they may interact with your body 55 EVALUATION Thought Exercise - Combine your knowledge – Properties of chemicals – Work practices and control methods My educated judgment gives me an approximate exposure Exposure Assessment Qualitative vs. Quantitative The monitoring results give me an actual exposures 56 RECOGNITION EVALUATION (Qualitative) Qualitative Exposure Assessment Judgment on whether a worker will be exposed over the OEL or conservatively, ½ the OEL (action level) 57 EVALUATION (Qualitative) Assessing your risk of airborne exposure Risk is the chance or possibility of an adverse outcome You need to evaluate the risks to assess if your are potentially exposed to an environmental stressor over an occupational overexposure limit 58 EVALUATION (Qualitative) Airborne Exposure Assessment Health Effects (Exposure Limits) Physical state of matter Concentration Properties of physical state Quantity Used Length of Time Exposed Type of Work Performed Work Conditions Ventilation History of Overexposure Environmental Stressor Properties must be weighed against the Risks Factors 59 RECOGNITION EVALUATION (Qualitative) Stressor Properties Ask yourself: EXPOSURE LIMIT Is there an OEL? – – – – OSHA ACGIH NIOSH AIHA 100 ppm Do you know why the limit was set? 60 RECOGNITION EVALUATION (Qualitative) Stressor Properties Ask yourself: 8 Hr TWA 15 Min STEL 10 Min Ceiling What type of limit? – Combination – Different concentrations 61 RECOGNITION EVALUATION (Qualitative) Stressor Properties Ask yourself: • • • • • • • • 62 Does the substance emit vapors? Does it evaporate quickly? Is it a fine powder? Will it pour quickly? Is there a reaction by-product? It the mixture more toxic? Can I smell it? Is there an odor threshold? There are times that you can smell odors at concentrations many times lower than an exposure limit. Odor vs. toxicity • benzene – sweet and carcinogen • skunk – brutal and irritant Olfactory fatigue • hydrogen sulfide – now you smell it… now you don’t Warning properties • mercaptans added to natural gas to give the characteristic odor • carbon monoxide – no odor 63 Selected Odor Thresholds Chemical Odor Low Odor High Description Irritating Conc. Exposure Limit (ACGIH) Acetone 20 ppm 679 ppm Misty Chemical, Sweet 200 ppm 500 ppm –8 hr 750 ppm - STEL Benzene 1.4 ppm 85 ppm Sweet, solvent 2,800 ppm 0.5 ppm – 8 hr 2.5 ppm - STEL Ethyl Benzene 2.0 ppm 200 ppm Aromatic 200 ppm 100 ppm – 8 hr 125 ppm - STEL Hydrogen Sulfide 0.0005 ppm 0.01 ppm Rotten eggs 10 ppm 5 ppm – 8 hr 15 ppm - STEL Perchloroethylene 4.6 ppm 69 ppm Chlorinated solvent 200 ppm 25 ppm – 8 hr 100 ppm - STEL Toluene 2.0 ppm 40 ppm Rubbery, mothballs 200 ppm 50 ppm – 8 hr Xylene 0.08 ppm 40 ppm Sweet 100 ppm 100 ppm – 8 hr 150 ppm - STEL To be used as guidelines only Are subjective and differ from person to person RECOGNITION EVALUATION (Qualitative) Stressor Properties No OELs, ask: Other safety hazards? • Fire, explosion and/or corrosion risks • Potential for environmental contamination • Slip, trips, falls • Ergonomics • Heat stress • Cryogenics • Cuts 65 EVALUATION (Qualitative) Stressor Properties Ask yourself: • Whether you may be exposed over the OEL using Risk Factors as a guideline 66 EVALUATION (Qualitative) Risk Factors Ask yourself questions like: • How much chemical will be handled? • How long will I be exposed? • Will the type of work performed generate airborne chemicals? • Will the work involve exposure to physical agents? • Is there adequate ventilation? • Will the chemicals be handled outdoors vs. indoors? • Has their been an overexpose in the past? 67 EVALUATION (Qualitative) Risk Factors How much chemical will I handled? • Total amount, surface area, etc. – The larger the surface area the more vapors are evaporated • Quantity must be balanced against hazardous nature of the material • However: small quantities of highly toxic or reactive substances can create significant risk 68 EVALUATION (Qualitative) Risk Factors How long will I be exposed? • The shorter the work process the less exposure duration • However: a short amount of exposure to a highly toxic or reactive substance can create significant risk. 69 EVALUATION (Qualitative) Risk Factors Will the type of work performed generate a release? • Pouring • Mixing mixing • Transferring • What if I break a container • Outdoors – 70 Hot & sunny vs. cold & cloudy EVALUATION (Qualitative) Example Consolidating HPLC Waste Potential Ventilation •Contaminants 1-2 minutes per Task bottle Exposure Duration Bottles / Day VP OELs Why OEL? 200 ppm TWA 250 ppm STEL Skin Eye Irr. Headache s Methanol (40%) General Pour from collection container into 55 gal drum 1-2 minutes per bottle 4 127.2 mm Hg (77°) Acetonitrile (59%) General Pour from collection container into 55 gal drum 1-2 minutes per bottle 4 91.1 mm Hg (77°) 20 ppm Skin Systemic effects Various Analytes (1%) General Pour from collection container into 55 gal drum 1-2 minutes per bottle 4 Various Various Various What else would you ask? 71 EVALUATION (Qualitative) Risk Factors Is there adequate ventilation? Local Exhaust Ventilation (LEV) • Can remove airborne agent at the generation source and greatly reduce the airborne concentration General Ventilation • Less effective than LEV • Can reduce airborne concentration by dilution 72 EVALUATION (Qualitative) Risk Factors History of personnel being overexposed during this work task? • Look at OSHA Logs Is there a specific OSHA Regulation where you assume overexposure until proven otherwise? • Ask site ESH personnel • Ask workers about past projects with air sampling • Lead • Asbestos • Hexavalent Chromium 73 EVALUATION (Qualitative) Symptoms of Exposure Identify sign & symptoms of exposure. If you experience any of the listed signs and symptoms of overexposure then you may be overexposed. 74 EVALUATION (Qualitative) Common Acute Health Effects COUGHING FEEL DIZZY / LIGHT HEADED / NAUSEA HEADACHE LACRAMATION RASH NAUESA IRRITATION / BURNING TO NOSE & LUNGS SKIN IRRITANT 75 SKIN / RESPIRATORY SENSITIZATION EVALUATION (Qualitative) Waste streams and work procedures should be reviewed prior to handling Understand all or ask for review by and IH: • What are the waste characteristics? • At what concentrations? • Does the waste have an exposure limits? • How will the waste be handled? • What are the hazards of the material? • What types of controls are in place? • What happens if I spill the material? 76 EVALUATION (Qualitative) Summary Your educated and experienced judgment will help you to: • Determine if an exposure over ½ an OEL is likely • If air sampling is required • If controls are necessary 77 EVALUATION (Quantitative) Quantitative Exposure Assessment Must be conducted by an experienced Industrial Hygienist Measurement of the stressor for comparison to OELs 78 EVALUATION (Quantitative) Examples of things to consider Before collecting samples After collecting samples • • • • • • Determine the stressor What OEL(s) will I use What laboratory will I use Sampling & calibration equipment Sampling strategy • • • 79 How to interpret the results Determine recommendations for corrective actions based on results Document the monitoring results Inform the employee EVALUATION (Quantitative) More to consider WHO Maximum Risk vs. All Employees WHERE Personal vs. Area Sample WHEN Grab vs. Integrated Sample How Active vs. Passive vs. Direct Reading 80 EVALUATION (Quantitative) Results may demonstrate Above ½ OEL • Need for more effective engineering or PPE controls • The potential hazards of an operation • The need for safer work practices Below ½ OEL • • • • Relative safety of the operation Effectiveness of controls Effectiveness of safe work practices Company/regulatory compliance 81 CONTROLS Airborne Exposure Prevention • • Generation of airborne contaminants Contact with the body CONTROLS Hierarchy of Controls Change the process to eliminate hazard, use a less toxic chemical, use a less hazardous process etc. Transfer waste in fume hoods, safety interlocks, lead shielding, inert atmospheres, guarding, etc. Implement procedures and policies, train employees, post warning signs, etc. Safety glasses, goggles, chemical protective gloves and apron, face shield, lab coats, etc. 83 CONTROLS Combination of Controls Typically a combination of methods used simultaneously • • • • • • Fume hood Hood use training Chemical safety training Written SOP on specific procedure Gloves, eye protection, lab coat Waste disposal methods training CONTROLS Elimination / Substitution • Work with researchers to eliminate waste stream 85 CONTROLS Engineering - Remove or isolate the hazard • Use local exhaust snorkel • Transfer waste in lab exhaust hood or glove box • Use plastic vs. glass containers • Use bottle carriers • Sharps containers • Plastic lined container • Secondary containers CONTROLS Administrative • Material handling techniques • Limits on container size • RCRA / DOT requirements • Good housekeeping • No eating / drinking at worksite • Personal hygiene • Medical monitoring program 87 CONTROLS Personal Protective Equipment • Gloves • Lab coat / Apron / Tyvek® • Face shield / goggles • Respiratory protection • Proper removal /disposal • Decontamination 88 ANTICIPATION / RECOGNITIION Summary – Do your homework Toxicology / Health Effects – How material effects the body Routs of Entry – How it enters the body Exposure Limits - How much is allowed Physical Properties of Chemicals – How will it behave 89 HOW WILL IT BEHAVE Evaluation Summary – Qualitative vs. Quantitative What can you “predict", in general, what will happen to: • Particulates generated when a bottle breaks • The vapors of liquids when you pour off waste • A liquid when it is spilled • Mix different waste streams Do you need to sample? 90 CONTROLS Summary - Prevention • • Generation of airborne contaminants Contact with the body Thank You, Any Questions? 92